It was at Rice University that Smalley and his colleagues discovered fullerenes, the third known form of pure carbon (diamond and graphite are the other two known forms). Smalley had designed a laser supersonic cluster beam apparatus that could vaporize any material into a plasma of atoms and then be used to study the resulting clusters (aggregates of tens to many tens of atoms). On a visit to Smalley’s lab, Kroto realized that the technique might be used to simulate the chemical conditions in the atmosphere of carbon stars and so provide compelling evidence for his conjecture that the carbon chains originated in stars.

In a now-famous 11-day series of experiments conducted in September 1985 at Rice University by Kroto, Smalley, and Curl and their student coworkers James Heath, Yuan Liu, and Sean O’Brien, Smalley’s apparatus was used to simulate the chemistry in the atmosphere of giant stars by turning the vaporization laser onto graphite. The study not only confirmed that carbon chains could be produced but also showed, serendipitously, that a hitherto unknown carbon species containing 60 atoms formed spontaneously in relatively high abundance. The atoms of fullerenes are arranged in a closed shell. C60, the smallest stable fullerene molecule, consists of 60 carbon atoms that fit together to form a cage, with the bonds resembling the pattern of seams on a soccer ball. The molecule was given the name buckminsterfullerene, or buckyball, because its shape is similar to the geodesic domes designed by the American architect and theorist R. Buckminster Fuller.

A leading supporter of nanotechnology, Smalley played a key role in the establishment in 2000 of the National Nanotechnology Initiative, a federal research and development program.